EP2048166B1 - Fester titankatalysatorbestandteil, katalysator für die olefinpolymerisation und verfahren zur olefinpolymerisation - Google Patents
Fester titankatalysatorbestandteil, katalysator für die olefinpolymerisation und verfahren zur olefinpolymerisation Download PDFInfo
- Publication number
- EP2048166B1 EP2048166B1 EP07790753.3A EP07790753A EP2048166B1 EP 2048166 B1 EP2048166 B1 EP 2048166B1 EP 07790753 A EP07790753 A EP 07790753A EP 2048166 B1 EP2048166 B1 EP 2048166B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- group
- catalyst component
- compound
- carbon atoms
- solid titanium
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims description 149
- 238000006116 polymerization reaction Methods 0.000 title claims description 90
- 239000010936 titanium Substances 0.000 title claims description 88
- 229910052719 titanium Inorganic materials 0.000 title claims description 79
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims description 77
- 239000007787 solid Substances 0.000 title claims description 74
- 150000001336 alkenes Chemical class 0.000 title claims description 56
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims description 51
- 238000000034 method Methods 0.000 title claims description 35
- 239000004615 ingredient Substances 0.000 title 1
- 150000001875 compounds Chemical class 0.000 claims description 73
- 125000004432 carbon atom Chemical group C* 0.000 claims description 41
- 125000004122 cyclic group Chemical group 0.000 claims description 32
- 125000004185 ester group Chemical group 0.000 claims description 31
- 150000002430 hydrocarbons Chemical group 0.000 claims description 30
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 16
- 229910052749 magnesium Inorganic materials 0.000 claims description 14
- 150000002902 organometallic compounds Chemical class 0.000 claims description 13
- 229910052736 halogen Inorganic materials 0.000 claims description 12
- 150000002367 halogens Chemical class 0.000 claims description 12
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 11
- 239000011777 magnesium Substances 0.000 claims description 11
- 229910014455 Ca-Cb Inorganic materials 0.000 claims description 7
- 125000005843 halogen group Chemical group 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 239000010703 silicon Substances 0.000 claims description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 125000006841 cyclic skeleton Chemical group 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims description 6
- 239000011574 phosphorus Substances 0.000 claims description 6
- 125000004429 atom Chemical group 0.000 claims description 5
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 5
- 230000000737 periodic effect Effects 0.000 claims description 3
- -1 activated magnesium halide Chemical class 0.000 description 41
- 238000009826 distribution Methods 0.000 description 36
- 229920000098 polyolefin Polymers 0.000 description 31
- 229920000642 polymer Polymers 0.000 description 29
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 22
- 230000000694 effects Effects 0.000 description 22
- 150000002681 magnesium compounds Chemical class 0.000 description 22
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 13
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 13
- 150000003609 titanium compounds Chemical class 0.000 description 13
- 229910052739 hydrogen Inorganic materials 0.000 description 12
- 239000001257 hydrogen Substances 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- 239000004711 α-olefin Substances 0.000 description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 229920001155 polypropylene Polymers 0.000 description 10
- 239000004215 Carbon black (E152) Substances 0.000 description 9
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 9
- 229930195733 hydrocarbon Natural products 0.000 description 9
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 8
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 8
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 8
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 8
- 239000000460 chlorine Substances 0.000 description 8
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 8
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 7
- 239000005977 Ethylene Substances 0.000 description 7
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 7
- MGWAVDBGNNKXQV-UHFFFAOYSA-N diisobutyl phthalate Chemical compound CC(C)COC(=O)C1=CC=CC=C1C(=O)OCC(C)C MGWAVDBGNNKXQV-UHFFFAOYSA-N 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 125000001424 substituent group Chemical group 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 6
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 6
- 150000003961 organosilicon compounds Chemical class 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 125000001931 aliphatic group Chemical group 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 5
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 5
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 5
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- 239000004721 Polyphenylene oxide Substances 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 4
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 150000001733 carboxylic acid esters Chemical class 0.000 description 4
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 4
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 4
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 4
- 229910001629 magnesium chloride Inorganic materials 0.000 description 4
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 4
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 4
- 229920000570 polyether Polymers 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 4
- MEPSBRTXOHFWCF-UHFFFAOYSA-N (2-cyclohexyl-1,3-dimethoxypropan-2-yl)cyclohexane Chemical compound C1CCCCC1C(COC)(COC)C1CCCCC1 MEPSBRTXOHFWCF-UHFFFAOYSA-N 0.000 description 3
- DYLIWHYUXAJDOJ-OWOJBTEDSA-N (e)-4-(6-aminopurin-9-yl)but-2-en-1-ol Chemical compound NC1=NC=NC2=C1N=CN2C\C=C\CO DYLIWHYUXAJDOJ-OWOJBTEDSA-N 0.000 description 3
- RGHIYOCUMCUWAQ-UHFFFAOYSA-N 3,3-bis(methoxymethyl)-2,5-dimethylhexane Chemical compound COCC(COC)(CC(C)C)C(C)C RGHIYOCUMCUWAQ-UHFFFAOYSA-N 0.000 description 3
- BHPDSAAGSUWVMP-UHFFFAOYSA-N 3,3-bis(methoxymethyl)-2,6-dimethylheptane Chemical compound COCC(C(C)C)(COC)CCC(C)C BHPDSAAGSUWVMP-UHFFFAOYSA-N 0.000 description 3
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 3
- PVWCLOAAEFMTLH-UHFFFAOYSA-N 4,4-bis(methoxymethyl)-2,6-dimethylheptane Chemical compound COCC(COC)(CC(C)C)CC(C)C PVWCLOAAEFMTLH-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- ZVGIBQMBZHWERX-UHFFFAOYSA-N [2-(cyclohexylmethyl)-3-methoxy-2-(methoxymethyl)propyl]cyclohexane Chemical compound C1CCCCC1CC(COC)(COC)CC1CCCCC1 ZVGIBQMBZHWERX-UHFFFAOYSA-N 0.000 description 3
- 150000001299 aldehydes Chemical class 0.000 description 3
- 125000002723 alicyclic group Chemical group 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- SJJCABYOVIHNPZ-UHFFFAOYSA-N cyclohexyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C1CCCCC1 SJJCABYOVIHNPZ-UHFFFAOYSA-N 0.000 description 3
- 150000001993 dienes Chemical class 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 150000003021 phthalic acid derivatives Chemical class 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 2
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 2
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 2
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- ZFAGXQVYYWOLNK-UHFFFAOYSA-N CCO[Mg] Chemical compound CCO[Mg] ZFAGXQVYYWOLNK-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- DMEGYFMYUHOHGS-UHFFFAOYSA-N cycloheptane Chemical compound C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 2
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- ZVMRWPHIZSSUKP-UHFFFAOYSA-N dicyclohexyl(dimethoxy)silane Chemical compound C1CCCCC1[Si](OC)(OC)C1CCCCC1 ZVMRWPHIZSSUKP-UHFFFAOYSA-N 0.000 description 2
- JWCYDYZLEAQGJJ-UHFFFAOYSA-N dicyclopentyl(dimethoxy)silane Chemical compound C1CCCC1[Si](OC)(OC)C1CCCC1 JWCYDYZLEAQGJJ-UHFFFAOYSA-N 0.000 description 2
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 238000009775 high-speed stirring Methods 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methylcycloheptane Chemical compound CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- VAMFXQBUQXONLZ-UHFFFAOYSA-N n-alpha-eicosene Natural products CCCCCCCCCCCCCCCCCCC=C VAMFXQBUQXONLZ-UHFFFAOYSA-N 0.000 description 2
- KOFGHHIZTRGVAF-UHFFFAOYSA-N n-ethyl-n-triethoxysilylethanamine Chemical compound CCO[Si](OCC)(OCC)N(CC)CC KOFGHHIZTRGVAF-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N o-dicarboxybenzene Natural products OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadec-1-ene Chemical compound CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000002685 polymerization catalyst Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- XBFJAVXCNXDMBH-UHFFFAOYSA-N tetracyclo[6.2.1.1(3,6).0(2,7)]dodec-4-ene Chemical group C1C(C23)C=CC1C3C1CC2CC1 XBFJAVXCNXDMBH-UHFFFAOYSA-N 0.000 description 2
- HPOWOWTVWZELDK-UHFFFAOYSA-N (1,3-dimethoxy-2-methylpropan-2-yl)cyclohexane Chemical compound COCC(C)(COC)C1CCCCC1 HPOWOWTVWZELDK-UHFFFAOYSA-N 0.000 description 1
- KGWNCXDKGBGRNE-UHFFFAOYSA-N (1,5-dimethoxy-4-phenylpentan-2-yl)benzene Chemical compound C=1C=CC=CC=1C(COC)CC(COC)C1=CC=CC=C1 KGWNCXDKGBGRNE-UHFFFAOYSA-N 0.000 description 1
- CNWLBDIBXWDOLY-UHFFFAOYSA-N (1,5-dimethoxy-5-phenylhexan-2-yl)benzene Chemical compound C=1C=CC=CC=1C(COC)CCC(C)(OC)C1=CC=CC=C1 CNWLBDIBXWDOLY-UHFFFAOYSA-N 0.000 description 1
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 description 1
- USWVUBUQOUONFU-UHFFFAOYSA-N (3-cyclohexyl-1,4-diethoxybutan-2-yl)cyclohexane Chemical compound C1CCCCC1C(COCC)C(COCC)C1CCCCC1 USWVUBUQOUONFU-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- PTOOVEFBMMTMJP-UHFFFAOYSA-N 1,3-dimethoxy-2-(methoxymethyl)-2-methylpropane Chemical compound COCC(C)(COC)COC PTOOVEFBMMTMJP-UHFFFAOYSA-N 0.000 description 1
- 229940106006 1-eicosene Drugs 0.000 description 1
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- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- ASEHKQZNVUOPRW-UHFFFAOYSA-N tert-butyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C(C)(C)C ASEHKQZNVUOPRW-UHFFFAOYSA-N 0.000 description 1
- JHVNMGWNEQGGDU-UHFFFAOYSA-N tert-butyl-diethoxy-methylsilane Chemical compound CCO[Si](C)(C(C)(C)C)OCC JHVNMGWNEQGGDU-UHFFFAOYSA-N 0.000 description 1
- NETBVGNWMHLXRP-UHFFFAOYSA-N tert-butyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C(C)(C)C NETBVGNWMHLXRP-UHFFFAOYSA-N 0.000 description 1
- YDLQKLWVKKFPII-UHFFFAOYSA-N timiperone Chemical compound C1=CC(F)=CC=C1C(=O)CCCN1CCC(N2C(NC3=CC=CC=C32)=S)CC1 YDLQKLWVKKFPII-UHFFFAOYSA-N 0.000 description 1
- 229950000809 timiperone Drugs 0.000 description 1
- UBZYKBZMAMTNKW-UHFFFAOYSA-J titanium tetrabromide Chemical compound Br[Ti](Br)(Br)Br UBZYKBZMAMTNKW-UHFFFAOYSA-J 0.000 description 1
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 1
- PTCWADDVLPYBBZ-UHFFFAOYSA-N tricyclopentylmethoxysilane Chemical compound C1CCCC1C(C1CCCC1)(O[SiH3])C1CCCC1 PTCWADDVLPYBBZ-UHFFFAOYSA-N 0.000 description 1
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- IOPAQHDEQBHWEB-UHFFFAOYSA-N trimethoxy-(2-methylcyclopentyl)silane Chemical compound CO[Si](OC)(OC)C1CCCC1C IOPAQHDEQBHWEB-UHFFFAOYSA-N 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Images
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- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
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- C08F4/654—Pretreating with metals or metal-containing compounds with magnesium or compounds thereof
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
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Definitions
- the present invention relates to a solid titanium catalyst component which is preferably used for the polymerization of an ⁇ -olefin having 3 or more carbon atoms. Further, the present invention relates to a catalyst for olefin polymerization containing the solid titanium catalyst component. Furthermore, the present invention relates to a method of olefin polymerization using the catalyst for olefin polymerization.
- a catalyst used for producing ethylene a homopolymer of an ⁇ -olefin or an olefin polymer such as an ethylene- ⁇ -olefin copolymer
- a catalyst containing a titanium compound supported on activated magnesium halide hereinafter, "homopolymerization” and “copolymerization” may be described as “polymerization”
- a catalyst for olefin polymerization there have been widely known a catalyst containing titanium tetrachloride and titanium trichloride which is referred to as a Ziegler-Natta catalyst, a catalyst composed of a solid titanium catalyst component composed of magnesium, titanium, halogen and an electron donor, and an organometallic compound.
- the latter catalyst shows high activity to the polymerization of an ⁇ -olefin such as propylene, and 1-butene in addition to ethylene.
- the resulting ⁇ -olefin polymer may have high stereoregularity.
- Patent Document 1 Japanese Patent Laid-Open Publication No. S57-63310
- a polymer obtained by using the catalyst frequently has a molecular weight distribution narrower than that of a polymer obtained by using a Ziegler-Natta catalyst. It is known that the polymer having a narrow molecular weight distribution tends to have "a low melt flowability", “a low melt tension”, “a poor moldability”, and "a slightly low rigidity". On the other hand, from the viewpoints of productivity improvement, and reduction in cost, there have been advanced various high speed molding technologies such as, for example, high speed stretching technologies for the purpose of improving the productivity of a stretched film.
- Patent Document 2 Japanese Patent Laid-Open Publication No. H05-170843 (Patent Document 2)
- Patent Document 2 Japanese Patent Laid-Open Publication No. H05-170843 (Patent Document 2)
- Patent Document 2 Japanese Patent Laid-Open Publication No. H05-170843
- Patent Document 2 Japanese Patent Laid-Open Publication No. H05-170843
- Patent Document 2 Japanese Patent Laid-Open Publication No. H05-170843
- Patent Document 2 Japanese Patent Laid-Open Publication No.
- Patent Document 3 H03-7703
- Patent Document 5 a catalyst using a succinic acid ester having an asymmetric carbon as the electron donor contained in a solid titanium catalyst component
- Patent Document 6 International Publication WO 2001/057099
- Patent Document 5 International Publication WO 2000/63261
- Patent Document 6 International Publication WO 2002/30998
- Patent Document 7 describes that there is a disclosure in Patent Documents 4 to 6 that a catalyst containing a carboxylic acid ester having a divalent or more valent ester group gives a polyolefin having a broad molecular weight distribution.
- the catalysts are catalysts which have an insufficient effect of broadening the molecular weight distribution of a olefin polymer, and according to the studies conducted by the present inventors, broaden the molecular weight distribution by increasing the content of the low molecular weight components.
- the catalysts there is an evaluation by the market that it is not said that these catalysts is insufficient in improvement of the melt tension of the olefin polymer.
- a catalyst capable of producing an olefin polymer having a molecular weight distribution broadened by a simpler process has been expected by the market.
- an olefin polymer having a broad molecular weight distribution is produced when a solid titanium catalyst component containing a specific polycarboxylic acid ester compound having a divalent or more valent ester group with an alicyclic structure is use, and thus have completed the present invention.
- a solid titanium catalyst component (I) of the present invention is characterized by containing titanium, magnesium, a halogen and a cyclic polyvalent ester group-containing compound (a) specified by the following formula (1).
- n is an integer of 5 to 10.
- C a -C a and C a -C b are C-C.
- a plurality of R 1 s are each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms.
- a plurality of Rs are each independently an atom or a group selected from a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, a nitrogen-containing group, an oxygen-containing group, a phosphorus-containing group, a halogen-containing group and a silicon-containing group, and may be mutually bonded to form a ring.
- a double bond may be contained in a skeleton of the ring formed by the mutual bonding of Rs.
- the number of carbon atoms constituting the skeleton of the ring is 5 to 10.
- At least one among the plurality of Rs directly bonding to C b is preferably a group other than a hydrogen atom.
- bonds between the carbon atoms in the cyclic skeleton are all preferably single bonds.
- the cyclic skeleton is preferably composed of six carbon atoms.
- cyclic polyvalent ester group-containing compound (a) a compound represented by the following formula (1a) is preferred.
- n is an integer of 5 to 10.
- the single bond (provided that the C a -C a bond and C a -C b bond are excluded) in the cyclic skeleton may be replaced by a double bond.
- a plurality of R 1 s are each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms.
- a plurality of Rs are each independently an atom or a group selected from a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, a nitrogen-containing group, an oxygen-containing group, a phosphorus-containing group, a halogen-containing group and a silicon-containing group, and may be mutually bonded to form a ring.
- a double bond may be contained in the skeleton of the ring formed by the mutual bonding of Rs.
- the number of carbon atoms constituting the skeleton of the ring is 5 to 10.
- the catalyst for olefin polymerization of the present invention is characterized by containing the solid titanium catalyst component (I) and an organometallic compound catalyst component (II) containing a metal element selected from Group I, Group II and Group XIII of the periodic table.
- the catalyst for olefin polymerization of the present invention may further contain an electron donor (III).
- the olefin polymerization method of the present invention is characterized in that the olefin polymerization is carried out in the presence of the catalyst for olefin polymerization.
- a solid titanium catalyst component, a catalyst for olefin polymerization and a method for producing an olefin polymer of the present invention are suitable for producing an olefin polymer having high stereoregularity and a broad molecular weight distribution with high activity.
- an olefin polymer that has, for example, excellent rigidity in addition to the moldability such as high speed stretchability and high speed moldability is expected to be produced.
- solid titanium catalyst component (I) a catalyst for olefin polymerization and a method for producing an olefin polymer according to the present invention.
- the solid titanium catalyst component (I) according to the present invention is characterized by containing titanium, magnesium, a halogen and a cyclic polyvalent ester group-containing compound (a).
- the cyclic polyvalent ester group-containing compound (a) is represented by the following formula (1).
- n is an integer of 5 to 10, preferably 5 to 7 and especially preferably 6.
- C a represents a carbon atom.
- C a -C a and C a -C b are C-C.
- a plurality of R 1 s are each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 2 to 8 carbon atoms, still more preferably 4 to 8 carbon atoms and particularly preferably 4 to 6 carbon atoms.
- the hydrocarbon group includes an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a hexyl group, a heptyl group, an octyl group, a 2-ethylhexyl group, a decyl group, a dodecyl group, a tetradecyl group, a hexadecyl group, an octadecyl group, and an eicosyl group, and among these, an n-butyl group, an isobutyl group, a hexyl group and an octyl group are preferred, and more preferred are an n-butyl group and an isobutyl group.
- a plurality of Rs are each independently an atom or a group selected from a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, a nitrogen-containing group, an oxygen-containing group, a phosphorus-containing group, a halogen-containing group and a silicon-containing group, and at least one of Rs is preferably a group other than a hydrogen atom.
- the hydrocarbon group having 1 to 20 carbon atoms includes an aliphatic hydrocarbon group, an alicyclic hydrocarbon group and an aromatic hydrocarbon group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, an n-pentyl group, a cyclopentyl group, an n-hexyl group, a cyclohexyl group, a vinyl group, a phenyl group, and an octyl group.
- an aliphatic hydrocarbon group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, an n-pentyl group, a cyclopentyl group, an n-hex
- an aliphatic hydrocarbon group is preferred, and specifically a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group and a sec-butyl group are preferred.
- Rs may be mutually bonded to form a ring and a double bond may be contained in the skeleton of the ring formed by mutually bonding Rs.
- the number of carbon atoms constituting the skeleton of the ring is 5 to 10.
- Such a skeleton of the ring includes a norbornane skeleton, and a tetracyclododecene skeleton.
- a plurality of Rs may be a carboxylic acid ester group, an alkoxy group, a siloxy group, an aldehyde group and an acetyl group, and a carbonyl structure-containing group such as an oxycarbonylalkyl group. These substituents preferably contain one or more hydrocarbon groups.
- the cyclic polyvalent ester group-containing compound (a) includes cyclohexyl-1,2-diacetate, cyclohexyl-1,2-dipropionate, cyclohexyl-1,2-dibutanate, cyclohexyl-1,2-dihexanate, cyclohexyl-1,2-dioctanate, cyclohexyl-1,2-didecanate, cyclohexyl-1,2-dibenzoate, cyclohexyl-1,2-ditoluate, cyclopentyl-1,2-diacetate, cyclopentyl-1,2-dibutanate, cyclopentyl-1,2-dibenzoate, cyclopentyl-1,2-ditoluate, cycloheptyl-1,2-diacetate, cycloheptyl-1,2-dibutanate, cycloheptyl-1,2-dibenzoate, cyclohept
- the cyclic polyvalent ester group-containing compound (a) includes, in addition to the dicarbonates described above, an asymmetric compound such as 1-oxycarbonylmethyl, 2-oxycarbonylbutyl-3,6-dimethylcyclohexane, 1-oxycarbonylmethyl-2-oxycarbonylbutylcyclohexane, 1-oxycarbonylmethyl-2-oxycarbonylphenylcyclohexane, and 1-oxycarbonylmethyl-2-oxycarbonylphenyl-3-methyl-6-propyl cyclohexane.
- an asymmetric compound such as 1-oxycarbonylmethyl, 2-oxycarbonylbutyl-3,6-dimethylcyclohexane, 1-oxycarbonylmethyl-2-oxycarbonylbutylcyclohexane, 1-oxycarbonylmethyl-2-oxycarbonylphenylcyclohexane, and 1-oxycarbonylmethyl-2-oxycarbonylphenyl-3-methyl-6-propyl cyclohexane.
- a compound in which R is a hydrocarbon group is preferable because a solid titanium catalyst component having high activity and stereoregularity tends to be easily obtained.
- a compound in which at least one of plural Rs directly bonding to C b is a group other than a hydrogen atom is preferable in that an olefin polymer having the same broad molecular weight distribution and higher stereoregularity with higher activity is obtained.
- the compound specifically includes
- the compounds having the diester structure described above there is a cis-, or trans- isomer derived from the plural OCOR 1 groups in the Formula (1), any of which has effects conforming to the purpose of the present invention and a compound having a higher content of the trans isomer is preferred.
- the compound having a higher content of the trans-isomer has not only the effect of broadening the molecular weight distribution but also higher activity and the tendency to have higher stereoregularity in the resulting polymer.
- cyclic polyvalent ester group-containing compound (a) a compound in which a substituent is bonded to a carbon adjacent to C a is preferred and a compound represented by the following formula (1a) is especially preferred.
- n, R 1 , R, C a -C a and C a -C b are the same as above.
- a compound in which at least one of plural Rs directly bonded to C b is a group other than a hydrogen atom is preferable in that an olefin polymer having the same broad molecular weight distribution and higher stereoregularity with higher activity is obtained.
- These compounds may be used alone or in combination with two or more kinds thereof.
- these cyclic polyvalent ester group-containing compounds (a) may be used in combination with a catalyst component (b) or catalyst component (c) which is described later as long as the objective of the present invention is not impaired.
- the cyclic polyvalent ester group-containing compound (a) may be formed during the process of preparing solid titanium catalyst component (I).
- the cyclic polyvalent ester group-containing compound (a) may be contained in the solid titanium catalyst component by providing a process of substantially bringing an anhydrous carboxylic acid or carboxylic acid dihalide corresponding to the catalyst component (a) into contact with the corresponding polyol.
- a polymer having a broad molecular weight distribution is obtained by a method for producing an olefin polymer of the present invention.
- the reason for this is unknown at present, but the following causes are assumed.
- a cyclic hydrocarbon structure forms a variety of steric structures such as a chair conformation, and a boat conformation. Further, when the cyclic structure has a substituent, the variation of a possible steric structure is further increased. In addition, if the C a -C a bond and C a -C b bond connecting multiple ester groups (OCOR 1 groups) is a single bond, the variation of a possible steric structure is increased. Since the cyclic hydrocarbon structure may form these various steric structures, various active species are formed on the solid titanium catalyst component (I).
- olefin polymers having various molecular weights may be produced at one time, that is, olefin polymers having broad molecular weight distributions may be produced.
- a magnesium compound and a titanium compound are used in addition to the cyclic polyvalent ester group-containing compound (a).
- the specific examples of the magnesium compound includes a well-known magnesium compound such as a halogenated magnesium such as magnesium chloride, and magnesium bromide; an alkoxymagnesium halide such as methoxymagnesium chloride, ethoxymagnesium chloride, and phenoxymagnesium chloride, an alkoxymagnesium such as ethoxymagnesium, isopropoxymagnesium, butoxymagnesium, and 2-ethylhexoxymagnesium; an aryloxymagnesium such as phenoxymagnesium; a magnesium carboxylate such as magnesium stearate.
- a well-known magnesium compound such as a halogenated magnesium such as magnesium chloride, and magnesium bromide
- an alkoxymagnesium halide such as methoxymagnesium chloride, ethoxymagnesium chloride, and phenoxymagnesium chloride, an alkoxymagnesium such as ethoxymagnesium, isopropoxymagnesium, butoxymagnesium
- magnesium compounds may be used alone or in combination with two or more kinds thereof.
- these magnesium compounds may be a complex or a composite compound with other metals, or a mixture with other metal compounds.
- a halogen-containing magnesium compound is preferred, and magnesium halide, especially magnesium chloride is preferably used.
- magnesium halide especially magnesium chloride is preferably used.
- an alkoxymagnesium such as ethoxymagnesium is preferably used.
- the magnesium compound may be the one derived from other materials, for example, the one obtained by bringing an organomagnesium compound such as a Grignard reagent into contact with titanium halide, silicon halide, or alcohol halide.
- the titanium compound includes, for example, a tetravalent titanium compound represented by the following formula: Ti (OR) g X 4-g R is a hydrocarbon group, X is a halogen atom and g satisfies the condition 0 ⁇ g ⁇ 4.
- the titanium compound includes a titanium tetrahalide such as TiCl 4 , and TiBr 4 ; an alkoxytitanium trihalide such as Ti (OCH 3 ) Cl 3 , Ti(OC 2 H 5 )Cl 3 , Ti(O-n-C 4 H 9 )Cl 3 , Ti(OC 2 H 5 )Br 3 , and Ti(O-isoC 4 H 9 )Br 3 ; an alkoxytitanium dihalide such as Ti(OCH 3 ) 2 Cl 2 , and Ti (OC 2 H 5 ) 2 Cl 2 ; an alkoxytitanium monohalide such as Ti(OCH 3 ) 3 Cl, Ti(O-n-C 4 H 9 ) 3 Cl, and Ti(OC 2 H 5 ) 3 Br; a tetraalkoxytitanium such as Ti (OCH 3 ) 4 , Ti (OC 2 H 5 ) 4 , Ti (OC 4 H 9 ) 4 , and Ti(OCH
- titanium tetrahalide is preferred, and particularly titanium tetrachloride is preferred.
- titanium compounds may be used alone or in combination of two or more kinds thereof.
- the magnesium compounds and titanium compounds described above include, for example, those as described in detail in Patent Document 1, or Patent Document 2.
- the specifically preferable method includes, for example, the following methods (P-1) to (P-4).
- the reaction temperature for the preparation of the solid titanium catalyst component (I) is preferably from -30 to 150°C, more preferably from -25 to 130°C and further more preferably from -25 to 120°C.
- the production of the solid titanium catalyst component may be carried out in the presence of a well-known medium where necessary.
- the medium includes an aromatic hydrocarbon such as toluene having some polarity, a well-known aliphatic hydrocarbon or alicyclic hydrocarbon compound such as heptane, octane, decane, and cyclohexane.
- an aromatic hydrocarbon such as toluene having some polarity
- a well-known aliphatic hydrocarbon or alicyclic hydrocarbon compound such as heptane, octane, decane, and cyclohexane.
- a preferred example is an aliphatic hydrocarbon.
- the effect of obtaining a polymer having a broad molecular weight distribution is highly compatible with the activity and stereoregularity of the resulting polymer.
- the catalyst component (b) used for the formation of the solid adduct or the liquid-state magnesium compound a well-known compound which can solubilize the magnesium compound in the temperature range of room temperature to approximately 300°C is preferred, and for example, an alcohol, an aldehyde, an amine, carboxylic acids and a mixture thereof, are preferred.
- these compounds include, for example, those as described in detail in Patent Document 1 or Patent Document 2.
- an aliphatic alcohol such as methanol, ethanol, propanol, butanol, isobutanol, ethylene glycol, 2-methylpentanol, 2-ethylbutanol, n-heptanol, n-octanol, 2-ethylhexanol, decanol, and dodecanol; an alicyclic alcohol such as cyclohexanol, and methylcyclohexanol; an aromatic alcohol such as benzyl alcohol, and methylbenzyl alcohol; an aliphatic alcohol having an alkoxy group such as n-butylcellosolve; and others.
- an aliphatic alcohol such as methanol, ethanol, propanol, butanol, isobutanol, ethylene glycol, 2-methylpentanol, 2-ethylbutanol, n-heptanol, n-octanol, 2-ethylhe
- the carboxylic acid includes organic carboxylic acids having 7 or more carbon atoms such as caprylic acid, and 2-ethylhexanoic acid.
- the aldehyde includes aldehydes having 7 or more carbon atoms such as capric aldehyde, and 2-ethylhexylaldehyde.
- the amine includes amines having 6 or more carbon atoms such as heptylamine, octylamine, nonylamine, laurylamine, and 2-ethylhexylamine.
- the alcohols are preferred, and particularly ethanol, propanol, butanol, isobutanol, hexanol, 2-ethylhexanol, and decanol are preferred.
- the used amounts of the magnesium compound and catalyst component (b) in preparing the solid adduct or liquid-state magnesium compound vary depending on the kinds thereof, or the contact conditions.
- the magnesium compound is used in an amount of 0.1 to 20 mol/liter and preferably 0.5 to 5 mol/liter per unit volume of the catalyst component (b).
- a medium which is inert to the solid adduct may also be used at the same time where necessary.
- the preferred example of the medium includes a well-known hydrocarbon compound such as heptane, octane, and decane.
- the composition ratio of the magnesium of the resulting solid adduct or the liquid-state magnesium compound to the catalyst component (b) varies depending on the kinds of the compound to be used and thus cannot be generally defined.
- the amount of the catalyst component (b) is in the range of preferably 2.0 moles or more, more preferably 2.2 moles or more, further more preferably 2. 6 moles or more and particularly preferably 2. 7 moles or more and 5 moles or less, based on one mole of magnesium in the magnesium compound.
- the solid titanium catalyst component (I) of the present invention may further contain an aromatic carboxylic acid ester and/or a compound having two or more ether linkages through a plurality of carbon atoms (hereinafter, also referred to as "catalyst component (c)").
- catalyst component (c) an aromatic carboxylic acid ester and/or a compound having two or more ether linkages through a plurality of carbon atoms
- the catalyst component (c) there may be used, without any limitation, a well-known aromatic carboxylic acid ester or a polyether compound, which is conventionally preferably used for an olefin polymerization catalyst, for example, the compounds as described in Patent Document 2, and Japanese Patent Laid-Open Publication No. 2001-354714 .
- the aromatic carboxylic acid ester specifically includes an aromatic polyvalent carboxylic acid ester such as phthalic acid esters, in addition to an aromatic carboxylic acid monoester such as a benzoic acid ester, and a toluic acid ester.
- an aromatic polyvalent carboxylic acid ester is preferred and a phthalic acid ester is more preferred.
- a phthalic acid alkyl ester such as ethyl phthalate, n-butyl phthalate, isobutyl phthalate, hexyl phthalate, and heptyl phthalate are preferred, and diisobutyl phthalate is particularly preferred.
- polyether compound more specifically a compound represented by the following formula (3) is included.
- m is an integer satisfying the condition 1 ⁇ m ⁇ 10 and preferably an integer satisfying the condition 3 ⁇ m ⁇ 10
- R 11 to R 36 are each independently a hydrogen atom or a substituent having at least one kind of element selected from carbon, hydrogen, oxygen, fluorine, chlorine, bromine, iodine, nitrogen, sulfur, phosphorus, boron and silicon.
- R 11 and R 12 may be the same or different from each other. Any of R 11 to R 36 , preferably R 11 and R 12 may form a ring other than a benzene ring in combination.
- 1,3-diethers are preferred, and particularly 2-isopropyl-2-isobutyl-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypropane and 2,2-bis(cyclohexylmethyl)-1,3-dimethoxypropane are preferred.
- These compounds may be used alone or in combination of two or more kinds thereof.
- the cyclic polyvalent ester group-containing compound (a), the catalyst component (b) and the catalyst component (c) belong to a component which is referred to as an electron donor by those skilled in the art. It is known that the electron donor component shows an effect of increasing stereoregularity of the resulting polymer, an effect of controlling the composition distribution of the resulting copolymer and an effect as a flocculant of controlling the particle shape and particle size of the catalyst particle, while maintaining the high activity of the catalyst.
- cyclic polyvalent ester group-containing compound (a) of the present invention also shows to have an effect of further controlling the molecular weight distribution by the electron donor.
- the halogen/titanium (atomic ratio) that is, the number of moles of halogen atoms/the number of moles of titanium atoms
- the halogen/titanium (atomic ratio) is 2 to 100 and preferably 4 to 90 desirably.
- the cyclic polyvalent ester group-containing compound (a)/titanium (molar ratio) (that is, the number of moles of the cyclic polyvalent ester group-containing compound (a) /the number of moles of titanium atoms) is 0.01 to 100 and preferably 0.2 to 10 desirably.
- the catalyst component (b)/titanium atoms (molar ratio) is 0 to 100 and preferably 0 to 10 desirably, and the catalyst component (c)/titanium atoms (molar ratio) is 0 to 100 and preferably 0 to 10 desirably.
- the magnesium/titanium (atomic ratio) (that is, the number of moles of magnesium atoms/the number of moles of titanium atoms) is 2 to 100 and preferably 4 to 50 desirably.
- the content of a component which may be contained in addition to the cyclic polyvalent ester group-containing compound (a), for example, the catalyst component (b) and the catalyst component (c) is preferably 20% by weight or less and more preferably 10% by weight or less, based on 100% by weight of the cyclic polyvalent ester group-containing compound (a).
- the conditions described in, for example, EP 585869 A1 (the specification of European Patent Application Publication No. 0585869 ), or Patent Document 2 may be preferably employed except that the cyclic polyvalent ester group-containing compound (a) is used.
- the catalyst for olefin polymerization according to the present invention is characterized by containing the solid titanium catalyst component (I) according to the present invention and an organometallic compound catalyst component (II) containing a metal element selected from Group I, Group II and Group XIII of the periodic table.
- organometallic compound catalyst component (II) a compound containing a metal of Group XIII, for example, an organoaluminum compound, a complex alkylated product of Group I metal and aluminum, an organometallic compound of a metal of Group II, may be used. Among these, an organoaluminum compound is preferred.
- organometallic compound catalyst component (II) As the specific examples of the organometallic compound catalyst component (II), the organometallic compound catalyst components described in well-known documents such as EP 585869A1 may be preferably mentioned.
- the catalyst for olefin polymerization of the present invention may contain the catalyst component (III) described already where necessary together with the organometallic compound catalyst component (II).
- the catalyst component (III) preferably includes an organosilicon compound.
- the organosilicon compound may be exemplified by a compound represented by the following general formula (4).
- R n Si(OR') 4-n (4) In the formula, R and R' are a hydrocarbon group, and n is an integer satisfying the condition 0 ⁇ n ⁇ 4.
- organosilicon compound represented by the general formula (4) there may be specifically used diisopropyldimethoxysilane, t-butylmethyldimethoxysilane, t-butylmethyldiethoxysilane, t-amylmethyldiethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, t-butyltriethoxysilane, phenyltriethoxysilane, cyclohexyltrimethoxysilane, cyclopentyltrimethoxysilane, 2-methylcyclopentyltrimethoxysilane, cyclopentyltriethoxysilane, dicyclopentyldimethoxysilane, dicyclopentyldiethoxysilane, tricyclopen
- vinyltriethoxysilane, diphenyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane and dicyclopentyldimethoxysilane are preferably used.
- organosilicon compound further includes a silane compound represented by the following formula (5) described in International Publication WO 2004/016662 .
- R a is a hydrocarbon group having 1 to 6 carbon atoms.
- R a includes an unsaturated or saturated aliphatic hydrocarbon group having 1 to 6 carbon atoms and particularly preferably includes a hydrocarbon group having 2 to 6 carbon atoms.
- R a specifically includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, an n-pentyl group, an isopentyl group, a cyclopentyl group, an n-hexyl group, and a cyclohexyl group, among which an ethyl group is particularly preferable.
- R b is a hydrocarbon group having 1 to 12 carbon atoms or a hydrogen atom and includes an unsaturated or saturated aliphatic hydrocarbon group having 1 to 12 carbon atoms, or a hydrogen atom.
- R b specifically includes a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, an n-pentyl group, an isopentyl group, a cyclopentyl group, an n-hexyl group, a cyclohexyl group, and an octyl group, among which an ethyl group is particularly preferable.
- R c is a hydrocarbon group having 1 to 12 carbon atoms and includes an unsaturated or saturated aliphatic hydrocarbon group having 1 to 12 carbon atoms, or a hydrogen atom.
- R c specifically includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, an n-pentyl group, an isopentyl group, a cyclopentyl group, an n-hexyl group, a cyclohexyl group, and an octyl group, among which an ethyl group is particularly preferable.
- the compound represented by the formula (5) specifically includes dimethylaminotriethoxysilane, diethylaminotriethoxysilane, diethylaminotrimethoxysilane, diethylaminotriethoxysilane, diethylaminotri-n-propoxysilane, di-n-propylaminotriethoxysilane, methyl-n-propylaminotriethoxysilane, t-butylaminotriethoxysilane, ethyl-n-propylaminotriethoxysilane, ethyl-isopropylaminotriethoxysilane and methylethylaminotriethoxysilane.
- organosilicon compound examples include a compound represented by the following formula (6).
- RN is a cyclic amino group
- the cyclic amino group includes, for example, a perhydroquinolino group, a perhydroisoquinolino group, a 1,2,3,4-tetrahydroquinolino group, a 1,2,3,4-tetrahydroisoquinolino group, and an octamethyleneimino group.
- organosilicon compounds may be used in combination of two or more kinds thereof.
- a polyether compound which is described as an example of the aromatic carboxylic acid ester and/or a compound having two or more ether linkages through a plurality of carbon atoms may be preferably mentioned.
- 1,3-diethers are preferred, and particularly 2-isopropyl-2-isobutyl-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypropane and 2,2-bis(cyclohexylmethyl)-1,3-dimethoxypropane are preferred.
- These compounds may be used alone or in combination of two or more kinds thereof.
- the catalyst for olefin polymerization of the present invention may contain other components useful for olefin polymerization where necessary, in addition to each component as mentioned above.
- the other component includes, for example, a support such as silica, an antistatic agent, a particle flocculating agent, a storage stabilizer and others.
- the olefin polymerization method according to the present invention is characterized in that the olefin polymerization is carried out using a catalyst for olefin polymerization of the present invention.
- the term "polymerization” may include the meaning of copolymerization such as random copolymerization, and block copolymerization, in addition to homopolymerization.
- the polymerization may also be carried out in the presence of a prepolymerization catalyst which is obtained by prepolymerization of an ⁇ -olefin in the presence of the catalyst for olefin polymerization of the present invention.
- This prepolymerization is carried out by prepolymerization of an ⁇ -olefin in an amount of 0.1 to 1000 g, preferably 0.3 to 500 g and particularly preferably 1 to 200 g, based on 1 g of the catalyst for olefin polymerization.
- a catalyst having a concentration higher than the catalyst concentration in the polymerization system may be used.
- the concentration of the solid titanium catalyst component (I) in the prepolymerization is desirably in the range of typically approximately 0.001 to 200 mmol, preferably approximately 0.01 to 50 mmol, and particularly preferably 0.1 to 20 mmol, in terms of titanium atom, based on 1 liter of a liquid medium.
- the amount of the organometallic compound catalyst component (II) in the prepolymerization may be such that 0.1 to 1000 g and preferably 0.3 to 500 g of the polymer is produced based on 1 g of the solid titanium catalyst component (I), and the amount is desirably typically approximately 0.1 to 300 mol, preferably approximately 0.5 to 100 mol, and particularly preferably 1 to 50 mol, based on 1 mol of the titanium atom in the solid titanium catalyst component (I).
- the catalyst component (III) may be used where necessary, and in this case, these components are used in an amount of 0.1 to 50 mol, preferably 0.5 to 30 mol, and more preferably 1 to 10 mol, based on 1 mol of the titanium atom in the solid titanium catalyst component (I).
- the prepolymerization may be carried out under a mild condition by adding an olefin and the catalyst components to an inert hydrocarbon medium.
- the inert hydrocarbon medium to be used there may be specifically mentioned an aliphatic hydrocarbon such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; an alicyclic hydrocarbon such as cycloheptane, methylcycloheptane, 4-cycloheptane, and methyl-4-cycloheptane; an aromatic hydrocarbon such as benzene, toluene, and xylene; a halogenated hydrocarbon such as ethylene chloride, chlorobenzene; a mixture thereof.
- an aliphatic hydrocarbon such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene
- an alicyclic hydrocarbon such as cycloheptane, methylcycloheptane, 4-cyclohept
- inert hydrocarbon media an aliphatic hydrocarbon is particularly preferably used.
- the prepolymerization is preferably carried out batchwise.
- the prepolymerization may be carried out by using an olefin itself as a solvent, or may be carried out in a state where there is substantially no solvent. In this case, the prepolymerization is preferably carried out continuously.
- the olefin used in the prepolymerization may be the same or different from that used in the polymerization described later, and specifically propylene is preferred.
- the temperature at the time of prepolymerization is desirably in the range of typically approximately -20 to +100°C, preferably approximately -20 to +80°C and more preferably 0 to +40°C.
- an ⁇ -olefin having 3 to 20 carbon atoms for example, a linear olefin such as propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene; and a branched olefin such as 4-methyl-1-pentene, 3-methyl-1-pentene, and 3-methyl-1-butene, and preferably propylene, 1-butene, 1-pentene, 4-methyl-1-pentene and 3-methyl-1-butene are used. Further, particularly propylene, 1-butene, 4-methyl-1-pentene and 3-methyl-1-butene are preferred from the viewpoint that the advantages of a polymer having a broader molecular
- Ethylene; an aromatic vinyl compound such as styrene, and allylbenzene; an alicyclic vinyl compound such as vinylcyclohexane, and vinylcycloheptane may be also used together with these ⁇ -olefins.
- a compound having a polyunsaturated bond such as conjugated dienes or nonconjugated dienes, for example, dienes such as cyclopentene, cycloheptene, norbornene, tetracyclododecene, isoprene, and butadiene may be also used as a polymerization raw material together with ethylene and an ⁇ -olefin.
- dienes such as cyclopentene, cycloheptene, norbornene, tetracyclododecene, isoprene, and butadiene may be also used as a polymerization raw material together with ethylene and an ⁇ -olefin.
- these compounds may be used
- ethylene and an aromatic vinyl compound are preferred.
- the other olefins such as ethylene may be used in combination if used in a small amount, for example, 10% by weight or less and preferably 5% by weight or less, based on 100% by weight of the total amount of olefins.
- the prepolymerization and the polymerization may be carried out by any of liquid phase polymerization such as bulk polymerization, solution polymerization, and suspension polymerization, or vapor phase polymerization.
- an inert hydrocarbon used at the time of the prepolymerization or an olefin which is liquid at a reaction temperature may be used as a reaction solvent.
- the solid titanium catalyst component (I) is used in an amount of usually approximately 0.0001 to 0.5 mmol and preferably about 0.005 to 0.1 mmol, in terms of titanium atom, based on 1 liter of the polymerization volume.
- the organometallic compound catalyst component (II) is used in an amount of usually approximately 1 to 2000 mol, preferably approximately 5 to 500 mol, more preferably 10 to 350 mol, further more preferably 30 to 350 mol and particularly preferably 50 to 350 mol, based on 1 mol of the titanium atom in the prepolymerization catalyst component in the polymerization system.
- the catalyst component (III), if used, is used in an amount of 0.001 to 50 mol, preferably 0.01 to 30 mol and particularly preferably 0.05 to 20 mol, based on the amount of the organometallic compound catalyst component (II).
- the molecular weight of the resulting polymer may be controlled and a polymer with a high melt flow rate is obtained.
- the polymerization temperature of an olefin is in the range of usually approximately 20 to 200°C, preferably approximately 30 to 100°C and more preferably 50 to 90°C.
- the pressure is set to be in the range of usually normal pressure to 100 kgf/cm 2 (9.8 MPa) and preferably approximately 2 to 50 kgf/cm 2 (0.20 to 4.9 MPa).
- the polymerization may be carried out by any of batchwise process, semi-continuous process and continuous process. Further, the polymerization may be carried out in two or more stages by changing the reaction conditions. When the multi-stage polymerization is carried out, the molecular weight distribution of the olefin polymer may further be broadened.
- the olefin polymer thus obtained may be any one of a homopolymer, a random copolymer, or a block copolymer.
- a propylene polymer with high stereoregularity which has a content of the decane-insoluble components of 70% or more, preferably 85% or more and particularly preferably 90% or more may be obtained.
- a polyolefin, in particular polypropylene having a broad molecular weight distribution may be obtained even when the polymerization is carried out in a small number of stages, for example, a single stage rather than a multi-stage method.
- the olefin polymerization method of the present invention is particularly characterized in that an olefin polymer having a higher ratio of the high molecular weight components and a lower ratio of the low molecular weight components (referred to as "sticky components") may frequently be obtained as compared with a conventional olefin polymer having an equivalent melt flow rate (MFR).
- MFR equivalent melt flow rate
- the conventional polypropylene which is obtained by using a solid titanium catalyst component containing magnesium, titanium, halogen and an electron donor, generally has an Mw/Mn value of 5 or less and an Mz/Mw value of less than 4, which are indices of the molecular weight distribution as determined by GPC measurement, for example, in the region where it has an MFR of 1 to 10 g/10 min.
- an olefin polymer having an Mw/Mn value of 6 to 30 and preferably 7 to 20 may be obtained under the same polymerization conditions as described above.
- an olefin polymer having an Mz/Mw value of preferably 4 to 15 and more preferably 4. 5 to 10 may be obtained.
- a polymer having a high Mz/Mw value is frequently obtained.
- a polypropylene having a high Mw/Mn value is excellent in moldability and rigidity.
- a high Mz/Mw value indicates a high content of high molecular weight components, and it is expected that the resulting polypropylene is likely to have a high melt tension and excellent moldability.
- a polymer having a broad molecular weight distribution without carrying out the multi-stage polymerization may be obtained, therefore, the polymer production equipment may be made to be simpler.
- the conventional multi-stage polymerization it is expected that a polymer more excellent in melt tension and moldability may be obtained.
- the polymers obtained by the olefin polymerization method of the present invention are a mixture of polymers having different molecular weights in the extremely broad range of molecular weights in a catalytic level, that is, in a nano-level, they are expected to have high melt tension and excellent moldability.
- the bulk density, the melt flow rate, the content of the decane-soluble (insoluble) components, the molecular weight distribution of the propylene polymer were measured by the methods described below.
- the bulk density was measured in accordance with JIS K-6721.
- melt flow rate was measured in accordance with ASTM D 1238E at a measurement temperature of 230°C in the case of a propylene polymer, and 260°C in the case of a 4-methyl-1-pentene polymer.
- the Mw/Mn value and the Mz/Mw value were calculated by analyzing the chromatogram obtained by the measurement under the following conditions using a well-known method.
- the measurement time per one sample was 60 minutes.
- the compound corresponding to the cyclic polyvalent ester group-containing compound (a) of the present invention a synthetic compound manufactured by Azuma Co., Ltd. was used unless otherwise specifically mentioned.
- the purity of cis and trans isomers was 95% or more.
- the suspension was transferred to a 2-liter glass flask (equipped with a stirrer) which was previously charged with 1 liter of purified decane precooled to -10°C by using a Teflon (registered trade mark) tube having an inner diameter of 5 mm under high speed stirring so as not to generate precipitates.
- the solid generated by the transportation of the liquid was filtered and was sufficiently washed with purified n-hexane to obtain a solid adduct in which 2.8 mol of ethanol is coordinated to 1 mol of magnesium chloride.
- a solid titanium catalyst component (A) was obtained by the operations described above.
- the activity, MFR, amount of the decane-insoluble components, bulk density and molecular weight distribution (Mw/Mn and Mz/Mw) are shown in Table 1.
- a solid titanium catalyst component (B) was obtained in the same manner as in Example 1 except for using cyclohexyl-1,2-dibenzoate (CH) instead of 3,6-dimethylcyclohexyl-1,2-dibenzoate.
- the propylene polymerization was carried out in the same manner as in Example 1 except for using the solid titanium catalyst component (B) instead of the solid titanium catalyst component (A). The results are shown in Table 1.
- a solid titanium catalyst component (C) was obtained in the same manner as in Example 1 except that 0.15 mmol of diisobutyl phthalate (DIPB) (reagent of special grade, manufactured by Wako Pure Chemical Industries, Ltd.) based on 1 mol of magnesium atom was used instead of 3,6-dimethylcyclohexyl-1,2-dibenzoate, the reaction at 120°C was changed to 90 minutes and the reaction at 130°C was changed to 45 minutes.
- DIPB diisobutyl phthalate
- an olefin polymer having a broader molecular weight distribution as compared with an olefin polymerization catalyst containing a solid titanium catalyst component of the Comparative Examples which has been conventionally used is obtained.
- Such an olefin polymer is also advantageous in obtaining a resin having high melt flowability that is recently desired in the application, for example, of the injection molding for automobiles.
- Fig.1 The relationship between the used amount of hydrogen and MFR in the results described above is shown in Fig.1 . It has been known by those skilled in the art that the relationship between the used amount of hydrogen and MFR shows an excellent linearity on a graph when their respective logarithms are plotted. It is shown that when the multi-stage polymerization is carried out for the purpose of further broadening the molecular weight distribution, a catalyst having a steep slope on the graph may significantly change the molecular weight with a small change in the used amount of hydrogen. That is, it is advantageous for broadening the molecular weight distribution.
- the solid titanium catalyst component containing 3,6-dimethylcyclohexyl-1,2-dibenzoate is advantageous for further broadening the molecular weight distribution especially in the multi-stage polymerization and is also more preferable in that the results with high activity and high stereoregurality are obtained.
- an olefin polymer having an extremely broad molecular weight distribution may be obtained.
- a solid titanium catalyst component containing a cyclic polyvalent ester group-containing compound having a substituent in the cyclic portion is used, an olefin polymer having the same broad molecular weight distribution and higher stereoregularity with extremely high activity may be obtained, and it is advantageous in obtaining an olefin polymer having a broader molecular weight distribution when a multi-stage polymerization is employed at the same time.
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Claims (8)
- Fester Titankatalysatorbestandteil (I), umfassend Titan, Magnesium, Halogen und eine zyklische polyvalente Estergruppen-enthaltende Verbindung (a), dargestellt durch die folgende Formel (1):
- Fester Titankatalysatorbestandteil (I) nach Anspruch 1, wobei mindestens eines von der Vielzahl von direkt mit Cb verbundenen R eine andere Gruppe als ein Wasserstoffatom in der Formel (1) darstellt.
- Fester Titankatalysatorbestandteil (I) nach entweder Anspruch 1 oder Anspruch 2, wobei Bindungen zwischen Kohlenstoffatomen in dem zyklischen Gerüst alle Einfachbindungen in der Formel (1) darstellen.
- Fester Titankatalysatorbestandteil (I) nach einem beliebigen der Ansprüche 1 bis 3, wobei das zyklische Gerüst aus sechs Kohlenstoffatomen in der Formel (1) zusammengesetzt ist.
- Fester Titankatalysatorbestandteil (I) nach einem beliebigen der Ansprüche 1 bis 4, wobei die zyklische polyvalente Estergruppen-enthaltende Verbindung (a) eine Verbindung ist, dargestellt durch die folgende Formel (1a):
- Katalysator zur Olefinpolymerisation, umfassend:den festen Titankatalysatorbestandteil (I) gemäß einem beliebigen der Ansprüche 1 bis 5; undeinen organometallischen Verbindungskatalysatorbestandteil (II), enthaltend ein Metallelement ausgewählt aus der Gruppe I, Gruppe II und Gruppe XIII des Periodensystems.
- Katalysator zur Olefinpolymerisation nach Anspruch 6, des weiteren enthaltend einen Elektronendonor (III).
- Olefinpolymerisationsverfahren, umfassend das Durchführen von Olefinpolymerisation in Gegenwart des Katalysators zur Olefinpolymerisation gemäß Anspruch 6 oder 7.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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JP2006195732 | 2006-07-18 | ||
PCT/JP2007/063972 WO2008010459A1 (fr) | 2006-07-18 | 2007-07-13 | Ingrédient catalyseur au titane solide, catalyseur de polymérisation d'oléfine, et procédé de polymérisation d'oléfine |
Publications (3)
Publication Number | Publication Date |
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EP2048166A1 EP2048166A1 (de) | 2009-04-15 |
EP2048166A4 EP2048166A4 (de) | 2013-02-20 |
EP2048166B1 true EP2048166B1 (de) | 2014-02-26 |
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP07790753.3A Active EP2048166B1 (de) | 2006-07-18 | 2007-07-13 | Fester titankatalysatorbestandteil, katalysator für die olefinpolymerisation und verfahren zur olefinpolymerisation |
Country Status (7)
Country | Link |
---|---|
US (1) | US20090203855A1 (de) |
EP (1) | EP2048166B1 (de) |
JP (1) | JP5479734B2 (de) |
KR (2) | KR20090034984A (de) |
CN (1) | CN101490101B (de) |
TW (1) | TW200829615A (de) |
WO (1) | WO2008010459A1 (de) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
RU2502746C2 (ru) | 2008-12-31 | 2013-12-27 | ДАУ ГЛОБАЛ ТЕКНОЛОДЖИЗ ЭлЭлСи | Прокаталитическая композиция с замещенным 1,2-фениленовым ароматическим сложнодиэфирным внутренним донором и способ |
KR101695995B1 (ko) * | 2008-12-31 | 2017-01-12 | 더블유.알. 그레이스 앤드 캄파니-콘. | 향상된 전촉매 조성물 및 방법 |
CN104736576B (zh) | 2012-10-25 | 2017-07-11 | 普瑞曼聚合物株式会社 | 多微孔膜用聚丙烯 |
CN107406644A (zh) | 2015-03-31 | 2017-11-28 | 普瑞曼聚合物株式会社 | 膜电容器用聚丙烯、膜电容器用双轴拉伸膜、膜电容器以及这些的制造方法 |
JP7466661B2 (ja) | 2020-08-26 | 2024-04-12 | 三井化学株式会社 | 固体状チタン触媒成分、オレフィン重合用触媒、オレフィンの重合方法およびプロピレン重合体 |
CN116635432A (zh) | 2020-12-21 | 2023-08-22 | 三井化学株式会社 | 固体状钛催化剂成分、烯烃聚合用催化剂、烯烃的聚合方法和丙烯聚合物 |
Family Cites Families (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
IT1209255B (it) * | 1980-08-13 | 1989-07-16 | Montedison Spa | Catalizzatori per la polimerizzazione di olefine. |
JP2825909B2 (ja) | 1989-03-02 | 1998-11-18 | 三井化学株式会社 | オレフィンの重合方法およびオレフィン重合用触媒 |
CA2011188C (en) * | 1989-03-02 | 2000-01-18 | Naoshi Ishimaru | Process for polymerizing olefins and catalyst for polymerizing olefins |
JP3476793B2 (ja) | 1990-04-13 | 2003-12-10 | 三井化学株式会社 | オレフィン重合用固体状チタン触媒成分、オレフィン重合用触媒およびオレフィンの重合方法 |
JP3088164B2 (ja) | 1991-12-20 | 2000-09-18 | 三井化学株式会社 | プロピレン系ブロック共重合体の製造方法 |
JP3280477B2 (ja) | 1992-08-31 | 2002-05-13 | 三井化学株式会社 | オレフィン重合用固体状チタン触媒成分の調製方法 |
JP3306119B2 (ja) * | 1992-09-01 | 2002-07-24 | 出光石油化学株式会社 | オレフィン重合体の製造方法 |
JP3489889B2 (ja) * | 1994-12-01 | 2004-01-26 | 昭和電工株式会社 | オレフィン重合用固体触媒成分の製造方法、オレフィン重合用触媒及びオレフィン重合体の製造方法 |
MY125673A (en) * | 1996-06-10 | 2006-08-30 | Mitsui Chemicals Inc | Solid titanium catalyst component for olefin polymerization,process for preparing the same, olefin plymerization catalyst containing the catalyst component and olefin polymerization process using thecatalyst |
ES2269135T3 (es) | 1999-04-15 | 2007-04-01 | Basell Poliolefine Italia S.R.L. | Componentes y catalizadores para la polimerizacion de olefinas. |
WO2002030998A1 (en) | 2000-10-13 | 2002-04-18 | Basell Technology Company B.V. | Catalyst components for the polymerization of olefins |
EP1165633B1 (de) | 2000-02-02 | 2004-07-14 | Basell Poliolefine Italia S.p.A. | Komponente und katalysatoren für polymerisation von olefine |
JP2001329013A (ja) * | 2000-05-24 | 2001-11-27 | Toho Titanium Co Ltd | オレフィン類重合用固体触媒成分および触媒 |
DE60126952T2 (de) * | 2000-07-03 | 2007-10-31 | Mitsui Chemicals, Inc. | Butencopolymer, harzzusammensetzung die dieses enthält sowie formmassen aus der zusammensetzung |
CN1169845C (zh) * | 2002-02-07 | 2004-10-06 | 中国石油化工股份有限公司 | 用于烯烃聚合的固体催化剂组分和含该催化剂组分的催化剂及其应用 |
WO2004005359A1 (en) * | 2002-07-02 | 2004-01-15 | Basell Poliolefine Italia S.P.A. | Catalyst system for the polymerization of olefins |
WO2004016662A1 (ja) | 2002-08-19 | 2004-02-26 | Ube Industries, Ltd. | α−オレフィンの重合又は共重合に用いられるα−オレフィンの重合又は重合用触媒、その触媒成分及びその触媒を用いたα−オレフィン重合方法 |
ES2537554T3 (es) * | 2005-01-19 | 2015-06-09 | Mitsui Chemicals, Inc. | Componente catalizador de titanio sólido, catalizador para la polimerización de olefina y proceso para producir polímeros de olefina |
-
2007
- 2007-07-13 EP EP07790753.3A patent/EP2048166B1/de active Active
- 2007-07-13 KR KR1020097003221A patent/KR20090034984A/ko active Application Filing
- 2007-07-13 WO PCT/JP2007/063972 patent/WO2008010459A1/ja active Application Filing
- 2007-07-13 JP JP2008525847A patent/JP5479734B2/ja active Active
- 2007-07-13 US US12/309,319 patent/US20090203855A1/en not_active Abandoned
- 2007-07-13 KR KR1020117028063A patent/KR20110134522A/ko not_active Application Discontinuation
- 2007-07-13 CN CN2007800266855A patent/CN101490101B/zh active Active
- 2007-07-18 TW TW096126110A patent/TW200829615A/zh unknown
Also Published As
Publication number | Publication date |
---|---|
KR20110134522A (ko) | 2011-12-14 |
US20090203855A1 (en) | 2009-08-13 |
KR20090034984A (ko) | 2009-04-08 |
EP2048166A4 (de) | 2013-02-20 |
JP5479734B2 (ja) | 2014-04-23 |
EP2048166A1 (de) | 2009-04-15 |
CN101490101B (zh) | 2011-11-02 |
WO2008010459A1 (fr) | 2008-01-24 |
JPWO2008010459A1 (ja) | 2009-12-17 |
TW200829615A (en) | 2008-07-16 |
CN101490101A (zh) | 2009-07-22 |
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